Polyethylene glycol esters of acyloxycarboxylic acids



Patented Nov. 6 1951 UNITED s rATEs PATENT OFFICE zfisrsnor V roigriairiifii'tltiiii GLYo'dn iisir'iiiis or ACYL'OXYCARBOXYLIC ACIDS Edward Mr-Filachione, Philadelphia, Pa, Martin L..F,ein, Riverside, N. J and Charles H. Fisher,

Abington, Pa; assignors to the United States of America as represented by the Secretary of Agriculture No Drawing Application 1m 18,1948, Serial No. 33,836

4ClaimS. "(ciao-4&4)

(Granted undi'gr the act of March 3, 1883, as amended April 30, 1928; 370 0. G. 757) l a i n smad nde fin s -2 .QI March 3-, 1883 as amended by the act oi April 30, 1928, and the invention herein described, if patented in any country, may be manufactured and used by or for the Government of the limited States of America for governmental purposes throughout the world without the payment to us of any royalty thereon. r V

This application is acontinuation in part oi our co-pending application, Serial No. 7"4' 0,;1'Z filed August 22, 1947, now Patent No. 2,5342%, the disclosure of which is incorporated herein by reference. 7 V I N This invention relates to polyethylene glycol esters of acylated hydroxycarboxylic acids and has among its objects the provision of suchesters and processes for their preparation, Other objects and advantages of the invention will beapparent from the description of the invention. We have found that polyethylene glycol esters of acyloxycarboxylic acids, which possess valu+ able properties as solvents, plasticizers and rnodi-j fying agents for plastic compositions, can be p'r pared by reacting a polyethylene glycol, or a polyethylene glycol estercontaining at least one unsubstituted hydroxyl group, with an ester of a hydroxycarboxylic acid, and treating the re sulting glycol ester, thus formed by alcoholysis, with an acylating agent. I

According to our invention, the polyethylene glycol, or polyethylene glycol ester containing at least one unsubstituted hydroxyl group is subjected to alcoholysis (ester interchange) by heat ing at reaction temperature with an alkyl ester of a hydroxycarboxylic acid, preferably in the presence of a reaction catalyst and with concurrent removal from the reaction mixture of the alkanol formed in the alcoholysis process. The products thus obtained are then acylated by interaction with an organic acylating agent to form polyethylene glycol esters corresponding to the general formula (3H1 CHi'O-R wherein n is an integer from 1 to 3, and at least one of the substituents R and R is the acyl radical of an aliphatic alpha-acyloxymonocar- 2 boaylic acid, and R may be a member of the group consisting of acyl radicals of saturated aliphatic mdnocarb'dicyl'ic acids containing from 5 to 18 carbon atoms and wherein a: is an integer and R and "n have the sain e significance as above.

The process ofv the present invention is applicable to polyethylene glycols corresponding to the general formula ea. eam:

wherein 'nis an integer from 1 to 3, and to the esters of these glycols which contain at least one unsubstituted hydroxyl group. Suitable esters include; for example, the monoesters of the above defined g'lycol's with saturated aliphatic monocarboicylic acids containing from 5 to 18 carbon atoms like caproic; caprylic, lauric, palmitic or stearic acid; or hydroxycarboxylic. acids like glyeolic or lactic acid and diesters'of saturated aliphatic dicarboxylic acids like succinic, adipic, sebac'ic, azelaic acid and the like.

Esters of hydroxycarboxylic acids adapted for use in thealcoholysis process are the lower alkyl esters, such as methyl, ethyl or propyl esters of the lower, saturated, aliphatic, alpha-hydroxy monocarboxylic acids, like glycolic, lactic and alpha-hydroxyisobutyric acid.

Sliltibi alcoholysis catalysts include acidic substances as sulfuric acid or toluene s'ulftn acid, well as other esteri'fication catalysts; as inetal alcoholates like aluminum ethoxide or propoxide. v p

The products of the alcoholysis reaction are acylated in a conventional manner by treatment with an organic acylating agent. Suitable acylating agents include ketene, anhydrides and halides of carboxylic acids like acetic anhydride, propionic anhydride, acetoxypropionyl chloride, pelargonyl chloride and the like.

Since in the alcoholysis process the alkyl esters of hydroxycarboxylic acids are capable of reacting not only with the alcohol groups of the glycol radicals but also with other hydroxyl groups of the reactants and reaction products, the process usually yields products comprising a number 5 of components. The composition of the products obtained and the molecular weight of the predominant constituents can be controlled within certain limits by varying proportions of the reactants, the duration of the alcoholysis process and the amount of alkylol removed from the reaction mixture.

The following Examples I through VIII are 11- lustrative of the preparation of the glycol esters of the invention:

EXAMPLE I Preparation of diethylene glycol glycolyl glycolate propionate having the formula EXAlVIPLE II Preparation of diethyene glycol pol lactate ro pionate The intermediate dipolylactate was prepared by heating, at atmospheric pressure, a mixture of 106 g. (1 mole) diethylene glycol, 625 g. (6 moles) methyl lactate and 2 g. p-toluene sulfonic acid (catalyst), and distilling methanol slowly as it was formed in the ester interchange reaction. The total hearing time was approximately 12 hours during which 135 cc. methanol was collected, 111 cc. being collected during the first 7 hours. After the reaction mixture had cooled to nearly room temperature, the flask was again heated under good vacuum to distill the excess methyl lactate and any other low-boiling materials.

The distillation residue consisting essentially of polylactate of diethylene glycol, had an index with a 2-foot Vigreaux-type distilling column. 77

g. of methanol were distilled from the reaction mixture over a period of about 5 hours while the temperature in the still-pot was gradually raised from 118 to 170 C. Excess methyl glycolate was then removed by maintaining the contents of the flask at about 100 C. under a vacuum of 2-3 mm. of mercury until distillation ceased. The distillation residue, consisting essentially of diethylene glycol glycolyl glycolate, was treated with apof refraction (N of 1.4525 and ester equivalent of 103.0. Theoretical ester equivalents are:

Diethylene glycol monolactate=178.l8 Diethylene glycol dilactate=125.12 Diethylene glycol dilactyllactate=98.5 Diethylene glycol lactate lactyllactate=107.44

The product, isolated as described in Example I above, was treated with 390 g. (3 moles) of propionic anhydride containing several drops of concentrated sulfuric acid as a catalyst. The anhydride was added in small portions and the reaction started after a short induction period when about one-third of the anhydride was addproximately2.2 moles propionic anhydride, which W n the flask temperature began o op.

and sodium bicarbonate, and finally with water containing a small amount of sodium chloride to inhibit formation of emulsions. The neutral ether solution was dried with anhydrous calcium sulfate and distilled under reduced pressure to the flask was warmed for about Me hour on a steam bath to assure completion of the reaction. Propionic acid and any other low-boiling products present were distilled under vacuum. Residual acidic components were washed out with dilute sodium bicarbonate solution and water. The product separated readily during the washing operation.

The final product, dried over anhydrous CaSO4 and filtered, was clear and pale strawcolored and had a refractive index (N of 1.4397. It consisted predominantly of diethylene glycol lactyllactate propionate having the formula:

CH-C- CHaCHr-F- The yield was approximately theoretical when based on a lactate averaging a molecular weight EXAMPLE III Preparation of diethylene glycol sebacate lactyl lactate acetate and propionate Diethylene glycol sebacate was prepared by re-' acting 202 g. (1 mole) sebacic acid with 265 g. (2.5- moles)" di'ethylene glycol using 1 ml. of concentrated sulfuric acid as the catalyst and 300 cc. benzene as the entraining agent. When the esterification reaction was completed, the en'- ethylene glycol d'i-alpha-acetoxypropionate) had.- a refractive index (N of 1.4460. The yield was 385 g.- r

Preparation; of tetrae'thylene glycol dilactcte dipr opimiate was prepared by the procedure described the foregoing example, using propionic anhydride as the acylating agent. g V

The final product, after washing with dilute aqueous sodium bicarbonateand water to remove residual acidity, had a refractive index (N 01- 1.4470. The yield was 390g.

EXAMPLE VI Prepdmtion o7- dz'ethylene glycol monolaurate poll/lactate pelargonate O I II acid formed during acylation and treatment with decolorizing carbon, the acylated product was washed acid-free.

The products. thus obtained had the following characteristics:

Diethylene glycolsebacatelactyl' lactate acetate N ?=I.448O d4 =1.l441 Ester equivalent-=92.1

Diethylene glycol sebacate lactyl lactate propionate Ester equivalent=100.3

EXAMPLE IV Preparation of tetraethylene glycol dilactate diacetate.

Diethylene glycol monolaurate polylactate was prepared by ester interchange reaction using 288 g. (1 mole)" diethylene glycol monolaur'ate, 416g. (4 mole) methyl lactate and l g. p-toluene sulfonic acid' (catalyst). After distilling the meth anol formed during the reaction, excess methyl lactate was removed under reduced pressure" as described in the foregoing" examples.

0.5 mole diethylene glycol monola'urate polylactate was treated'witli 0.5 mole pelargonyl' chloride in the presence of 200 cc. ethyl ether" and" 120 g. (1.5 mole) of pyridine. -The acylation was conducted below 15 C. with constant stirring.

On completion of the reaction, the pyridine hy drochloride precipitate was dissolved by addition of water and the aqueous solution separated from the oily layer consisting essenti'ally of diethylene glycol monolaurate polyl'actate pelargonate. The product so obtained was washed acid free with A mixture of 200 g. (1 mole) tetraethylene glycol, 416 g. (4 mole) methyl lactate and 1- g. ptoluene sulfonic acid was heated to distill 95 cc. of methanol over aperiod of about 5 hours while thetemperature of the reactionv mixture was gradually raised trom'125 to 165 C. The cata aqueous sodium chloride solution and had a ref-ractive index (N of 1.4449.

EXAMPLE VII Preparation of diethylene glycol dilactcte Z-ethylhexoate lyst was then neutralized with powdered calcium A mixture of 2 moles (212 g.) diethylene glycarbonate, and excess methyl lactate was distilled to col, 8 moles methyl lactate (832 g.) and 4 g.

fromthe reaction mixtureunder' reduced pres sure. The filtered distillation residue, consisting essentially oftetr aethylene glycol dilactate, was a pale straw-colored, water soluble substance? p-toluenesulfonic acid (catalyst), was heated at atmospheric pressure in a flask fitted with a 2-ioot Vigreaux-type distilling column. 164 ml. methanol was distilled from the reaction mixhaving-a refractive'index (N 3 of 1.4573; This ture over a period of about 5 hours, while the product was acy-lated intheusualmanner by addition of a slight excessof acetic anhydride contai'ningafew drops of concentrated sulfuric acid. The" acid catalyst was thenneutralized with caltemperature in the flask was gradually raised from 113 C. to 145 C. After allowing the flask to cool, the excess methyl lactate was distilledunder reduced pressure and the distillation resicium carbonata'and the reaction mixture was due was essentially diethylene glycol dilactate.

distilled under reduced pressureto remove acetic acid, acetic anhydride and asmallamount of lowboiling by-product's.

The" distillation residue, consisting essentially:

An 0.5 mole equivalent of this product was treated with 180 g. (1 mole and approximately 10% excess) 2-ethylhexoyl chloride by adding the chloride slowly to a cooled solution of the lactate of tetraethylene glycoldilactate d-iacetate (tetra in. pyridine (1 mole 10%) and 200 ml. ether.

8 When the reached was completed, the pyridine residue, consisting essentially of diethylene glycol hydrochloride was dissolved by adding 100 ml. adipate lactate was then treated with propionic water. The oil layer was separated and washed anhydride, using about a 1.05 equivalent of ansuccessively twice with very dilute HCl and six hydride to acylate all hydroxyl groups. After times with water. Benzene (200 ml.) was added distillation of the acid formed in the acylation, to the oil layer separated from the washing opthe product was dissolved in ether and washed eration. The mixture was then set up for distilacid-free with NaCl and NaHCOa solutions. The lation, the distillates in order being: ether, benether layer was then dried and the ether distilled. zene-water azeotrope and benzene. Residual The final product, diethylene glycol adipate lacben ene w s distilled y heating e fl k un 1 tate propionate had the following characterisreduced pressure. tics: N =l.4518; ester equivalent=94.0.

e u d t ylene glycol dilactate 2-eth- In the foregoing examples methyl glycolate and ylhexoate, was light in color, and'had a refracmethyl lactate can be replaced by equivalent tive index (N of 1.4440. amounts of other lower alkyl esters of alpha- EXAMPIE VIII hydroxymonocarboxylic acids, for instance, ethyl glycolate and ethyl lactate, respectively. Similar Preparation of triethylene glycol lactyl lactate products are also obtained by analogous methods propionate and pelargonate using lower alkyl esters of glycolic acid in place CH3 CH3 0 CH; cH-ooH-.- 3Hi0omoHzo0Hi0Hr-0-F- H CH;

H-F- t -F- H R i 0 0)(|JR R=CH3CHZ- R=CH3(CH2)7- A mixture of 1 mole (150 g.) triethylene glycol, of alkyl lactate and other 'acylating agents, like 6 moles (624 g.) methyl lactate and 1 g. of the halides or anhydrides of carboxylic acids.

p-toluenesulfonic acid monohydrate catalyst, was The following examples illustrate the use of the heated at atmospheric pressure in a flask fitted to compounds of the invention with synthetic plaswith a 2-ioot Vigreaux-type distilling column. tics, such as organic cellulose esters, cellulose 162 ml. methanol was distilled from the reaction ethers, and polyvinyl compounds, in the producmixture over a period of about 7 hours while the tion of plastic compositions.

temperature in the fiask rose from 124 C. to 175 C. After allowing the flask to cool, the excess :55 EXAMPLE X methyl lactate was distilled under reduced presg. of vinylchloride-acetate copolymer consure. The distillation residue, essentially tritaining approximately 95% polyvinyl chloride ethylene glycol lactyl lactate, was divided into and 5% polyvinyl acetate and 15 g. diethylene two equal portions, each approximately equivglycol dilactate Z-ethylhexoate of Example VII alenttoone-half mole. were blended on a mill. The milled sheet was One portion was treated with an equivalent molded at 300 F. and 12 T total pressure (about amount of propionic anhydride as described in 640 p. s. i.) for 2 minutes, removed from the mold other examples and the final product, triethylene and conditioned 64 hours at 77 F. and 50% R. H. glycol lactyl lactate propionate, was light in color, The resulting product was a tough, flexible sheet. N =1.4439. A similar product was obtained using triethyl- The other portion of triethylene glycol lactyl I ene glycol lactyl lactate pelargonate of Example lactate was treated with an equivalent amount of VIII as the plasticizing agent. pelargonyl chloride using a procedure similar to that described for acylation with acid chlorides EXAMPLE XI in other examples. The final product, triethyl- Plasticiied 00m1 08itiO11$--Ea0h 0f the P asene glycol lactyl lactate pelargonate, was light in ticizers listed in the table below was compatible l .N =1 4462, with ethyl and/or cellulose; acetate as indicated 1 in the table below. A plas icizer was considered EXAMPLE IX compatible if the final film was clear, dry and Preparation of diethylene glycol adipate lactate flexible.

propz'onate Cellulose acetate compatibility.The general 0 airba -0-oHr-oH20cH,cHro -OH-O-iL-CHr-CHM Diethylene glycol adipate was prepared by reprocedure to obtain a film containing approxiacting 292 g. (2 moles) adipic acid with 424 g. mately 25% plasticizer by weight was as follows: (4 moles) diethylene glycol using 1 ml. of con 0.33 g. of plasticizer was weighed into a small centrated sulfuric acid as the catalyst and 300 cc. glass-stoppered bottle. 20.6 cc. of a standard benzene as the entraining agent. When the acetone solution of cellulose acetate was added to esterification reaction was completed (approxithe bottle and the contents mixed well. (20.6 cc. mately 4 hours), the entraining agent was reacetone solution contained 1 g. cellulose acetate.) moved by distillation. One mole of diethylene The mixture was poured out on a clean glass plate glycol adipate (half the material prepared above) (6" x 8") to form a film. The plate was placed was then reacted with 5 moles methyl lactate, 7" into a box for slow evaporation of the solvent. with 1 gram p-toluenesulfonic acid (monohy- When the film appeared to be dry, the plate was drate) as catalyst. This ester-interchange reacplaced in an oven at 65 C. for about 4 hours to tion yielded approximately 2 moles methanol in insure evaporation of the solvent. When cool, one and one-half hours. The excess methyl lacthe film was removed from the glass plate and tate was distilled under reduced pressure, and the 76 examined for compatibility.

Ethyl cellulose compatibility-The general procedure to obtain a film containing approximately 25 plasticizer by weight was as follows: 0.33 g. of plasticizer was weighed into a small glassstoppered bottle. 15.5 cc. of a standard solution of ethyl cellulose was added to the bottle and the contents mixed well. (15.5 cc. solution contained 1 g. ethyl cellulose.) The mixture was poured out on a 6" x 8" glass plate and treated as described above.

Compatibility with- Compound Ethyl Cellulose Cellulose Acetate Tetraethylene glycol dilactate diproplonate.. 'Ietraethylene glycol dilactato diacetate Triethylene glycol lactyl lactate propionate Triethylene glycol lactyl lactate pclargonat :l: Diethylene glycol polylactate propionatm. Diethylene glycol polylactate pelargonatc. Diethylene glycol dilactate 2-ethylhexoate..-.. Diethylene glycol glycolyl glycolate propionate. Triethylene glycol monolaurate polylactate pclargonate Diethylene glycol sebacate lactyl lactate aceoiemyifi"giycbififiif "liht'yfieii propionate Diethylene glycol adipate lactate propionate compatible. =incompatible. =l==borderline compatibility Having described our invention we claim: 1. A polyethylene glycol ester corresponding to the formula wherein R is the acyl radical of a saturated aliphatic monocarboxylic acid containing from 2 to 3 carbon atoms.

2. The ester of claim 1 wherein R is propionyl.

3. A process comprising subjecting a compound ,selected from the group consisting of diethylene,

triethylene and tetraethylene glycols and saturated esters of said glycols containing at least one free hydroxyl group, to alcoholysis by heating it at reaction temperature with a lower alkyl ester of a lower, aliphatic alpha-hydroxymonocarboxylic acid with concurrent removal of the alcohol formed from the reaction mixture and then reacting the resulting glycol ester with an acylating agent.

4. A process comprising subjecting diethylene glycol sebacate to alcoholysis by heating it at reaction temperature with methyl lactate with concurrent removal of the alcohol formed from the reaction mixture, and then reacting the resulting glycol ester, which consists essentially of diethylene glycol sebacate lactyl lactate, with propionic anhydride as an acylating agent to produce diethylene glycol sebacate lactyl lactate propionate.

EDWARD M. FILACI-IIONE. MARTIN L. FEIN. CHARLES H. FISHER.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,072,102 Dreyfus Mar. 2, 1937 2,106,703 Cox et a1 Feb. 1, 1938 2,151,185 Carruthers Mar. 21, 1939 2,158,107 Carruthers May 16, 1939 2,196,758 Dickey et a1 Apr. 9, 1940 2,231,729 Meyer Feb. 11, 1941 2,290,128 Loder July 14, 1942 2,359,750 Collins Oct. 10, 1944 2,388,164 Loder Oct. 30, 1945 FOREIGN PATENTS Number Country Date 445,223 Great Britain Apr. 6, 1936 505,651 Great Britain May 8, 1939 

1. A POLYETHYLENE GLYCOL ESTER CORRESPONDING TO THE FORMULA 